Heterocyclic Bismuth(III) Dithiocarbamato Complexes as Single-Source Precursors for the Synthesis of Anisotropic Bi2 S3 Nanoparticles

Walter N Kun; Sixberth Mlowe; Linda D Nyamen; Peter T Ndifon; Mohammad A Malik; Orde Q Munro; Neerish Revaprasadu

doi:10.1002/chem.201602106

Heterocyclic Bismuth(III) Dithiocarbamato Complexes as Single-Source Precursors for the Synthesis of Anisotropic Bi2 S3 Nanoparticles

Chemistry. 2016 Sep 5;22(37):13127-35. doi: 10.1002/chem.201602106. Epub 2016 Aug 9.

Authors

Walter N Kun^{1

2}, Sixberth Mlowe¹, Linda D Nyamen², Peter T Ndifon², Mohammad A Malik^{1

3}, Orde Q Munro⁴, Neerish Revaprasadu⁵

Affiliations

¹ Department of Chemistry, University of Zululand, Private Bag X1001, Kwa-Dlangezwa, 3886, South Africa.
² Department of Inorganic Chemistry, University of Yaoundé I, P.O. Box 812, Yaoundé, Cameroon.
³ School of Materials, University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
⁴ Molecular Sciences Institute, School of Chemistry, University of Witwatersrand, P.O. WITS 2050, Johannesburg, South Africa.
⁵ Department of Chemistry, University of Zululand, Private Bag X1001, Kwa-Dlangezwa, 3886, South Africa. RevaprasaduN@unizulu.ac.za.

PMID: 27505614
DOI: 10.1002/chem.201602106

Abstract

New complexes catena-(μ2 -nitrato-O,O')bis(piperidinedithiocarbamato)bismuth(III) (1) and tetrakis(μ-nitrato)tetrakis[bis(tetrahydroquinolinedithiocarbamato)bismuth(III)] (2) were synthesised and characterised by elemental analysis, FTIR spectroscopy and thermogravimetric analysis. The single-crystal X-ray structures of 1 and 2 were determined. The coordination numbers of the Bi(III) ion are 8 for 1 and ≥6 for 2 when the experimental electron density for the nominal 6s(2) lone pair of electrons is included. Both complexes were used as single-source precursors for the synthesis of dodecylamine-, hexadecylamine-, oleylamine and tri-n-octylphosphine oxide-capped Bi2 S3 nanoparticles at different temperatures. UV/Vis spectra showed a blueshift in the absorbance band edge characteristic of a quantum size effect. High-quality, crystalline, long and short Bi2 S3 nanorods were obtained depending on the thermolysis temperature, which was varied from 190 to 270 °C. A general trend of increasing particle breadth with increasing reaction temperature and increasing length of the carbon chain of the amine (capping agent) was observed. Powder XRD patterns revealed the orthorhombic crystal structure of Bi2 S3 .

Keywords: S ligands; bismuth; chain structures; nanoparticles; sulfur.